Fungicidal compositions comprising A 10, 11 dihydrodibenzo {8 b,f{9 {0 azepine derivative

ABSTRACT

WHEREIN R represents hydrogen or alkyl of 1 through 5 carbon atoms, and R1 represents alkyl of 1 through 7 carbon atoms, are useful as fungicides.   New 10,11-dihydrodibenzo(b,f)azepines of the formula:

United States Patent [191 Fouch et al.

[ May 6,1975

[ FUNGICIDAL COMPOSITIONS COMPRISING A 10, ll DIHYDRODIBENZO [B,F] AZEPINE DERIVATIVE [75] Inventors: Jean Fouch, Bourg-la-Reine; Andre' Lger, Massy, both of France Related US. Application Data [62] Division of Ser. No. 48,450, June 22, i970, Pat. No.

[30} Foreign Application Priority Data June 24, 1969 France 69.21176 Apr. 9, 1970 France 70.12838 {521 US. Cl. 424/244 [51] Int. Cl A0ln 9/22 [58] Field of Search 424/244 [56] References Cited UNlTED STATES PATENTS 3,622,565 ll/l97l Fouch 424/244 OTHER PUBLICATIONS Chemical Abstracts, Vol. 68 (1968), p. 5942lv.

Primary ExaminerVincent D. Turner Attorney, Agent, or Firm-Stevens, Davis, Miller & Mosher [5 7] ABSTRACT New 10,1l-dihydrodibenzo[b,f]azepines of the formula:

IIH-COOH wherein R represents hydrogen or alkyl of 1 through 5 carbon atoms, and R represents alkyl of 1 through 7 carbon atoms, are useful as fungicides.

8 Claims, N0 Drawings 1 FUNGICIDAL COMPOSITIONS COMPRISING All], 11 DIIIYDRODIBENZO [B,F] AZEPINE DERIVATIVE This is a division of application Ser. No. 48,450, filed June 22, 1970 now U.S. Pat. No. 3,792,042.

This invention relates to new l0,1 1- dihydrodibenzoazepine derivatives. to a process for their preparation, and compositions containing them.

The 10,1 1-dihydrodibenzo[b,f]azepine derivatives of the present invention are those of the general formula:

Kill-(30012 wherein R represents a hydrogen atom or a straightor branched-chain alkyl radical containing 1 to 5 carbon atoms and R, represents a straightor branched-chain alkyl radical containing 1 to 7 carbon atoms.

According to a feature of the invention, the compounds of general formula I are prepared by the pro cess which comprises reacting a chloroformate of the general formula:

(wherein R is as hereinbefore defined) with a 10 amino-l0,ll-dihydrodibenzo[b,f]azepine of the general formula:

III

wherein R is as hereinbefore defined.

The reaction is generally carried out in an anhydrous medium, at a temperature between and +25C., either in an inert organic solvent such as an aromatic hydrocarbon (e.g, benzene or toluene), a chlorinated hydrocarbon (e.g. chloroform or dichloroethane), an ether (e.g. diethyl ether, diisopropyl ether, tetrahydrofuran or dioxan). or an amide (e.g. dimethylformamide), and in the presence of an inorganic base, preferably an alkali metal carbonate or bicarbonate, or an organic base such as triethylamine, or in a basic solvent such as pyridine. The process is advantageously carried out either in anhydrous benzene in the presence of triethylamine or simply in anhydrous pyridine.

In the case where the symbol R in formula III represents a hydrogen atom, only the NH grouping reacts under the reaction conditions and it is not necessary to protect the NH grouping of the ring.

The starting materials of general formula III can be prepared by reduction of an oxime of the general formula:

n l r I Iv (wherein R is as hereinbefore defined) by the action of sodium in a saturated primary aliphatic alcohol containing 2 to 6 carbon atoms, for example butanol, or by the action of sodium amalgam.

The compounds of general formula IV can be prepared from the corresponding ketones of the general formula:

I: l n 00H by reaction with a compound of the general formula:

wherein R represents a straightor branched-chain alkyl radical containing 1 to 5 carbon atoms, and X represents the acid residue of a reactive ester (e.g. a halogen atom), followed by hydrolysis of the resulting intermediate product of the formula:

VII

wherein R is as hereinbefore defined.

The 10,1l-dihydrodibenzoazepine derivatives obtained by the aforesaid process may optionally be purified by physical methods such as crystallisation or chromatography.

The dihydrodibenzoazepine derivatives of general formula I possess valuable fungicidal properties; they are particularly active against cucumber mildew (Erysiphe polyp/raga), against flax mildew (Erysiphe lint), against apple mildew (Podosphaera leucotricha), against rosebush mildew (Sphaerothica pannosu) and against mahonia mildew (Microsphaera berberidi's). Preferred compounds are those in which R represents a hydrogen atom or a methyl, ethyl or propyl radical, and R represents a straight-chain alkyl radical containing 3 to 6 carbon atoms and in particular -methyl-10- propoxy-carbonylamino-10,1 l-dihydrodibenzolb,- f]azepine, S-methyl-l0-butoxycarbonylamino-10,1ldihydrodibenzol l,flazepine, l0- hexyloxycarbonylarnino-10,1 l-dihydrobenzo[b,f]azepine, lO-propoxyearbonylamino- 1 0,1 l-dihydrodibenzo[b,f]azepine, l0-butoxycarbonylamino-10,11 dihydrodibenzo[b,f]azepine and 10- pentyloxycarbonylaminol 0,1 l-dihydrodibenzo[b,- flazepine.

The present invention also includes within its scope fungicidal compositions which contain, as the active ingredient, at least one 10,1l-dihydrodibenzoazepine derivative of general formula 1 in association with one or more diluents or adjuvants compatible with the compound(s) and suitable for use in agriculture. Preferably the compositions contain between 80 and 0.005% by weight of active compound.

The compositions may be solid if there is employed a powdered solid compatible diluent such as talc, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, absorbent charcoal, or a clay such as kaolin or bentonite. These solid compositions are preferably prepared by grinding the active compound with the solid diluent, or by impregnating the solid diluent with a solution of the compound in a volatile solvent, evaporating the solvent, and if necessary grinding the product so as to obtain a powder.

lnstead of a solid diluent, there may also be used a liquid in which the active compound is dissolved or dis persed. The compositions may thus take the form of suspensions, emulsions or solutions in organic or aqueous-organic media, for example acetophenone, aromatic hydrocarbons such as toluene or xylene, or mineral, animal or vegetable oils, or mixtures of these diluents. The compositions in the form of suspensions, emulsions or solutions may contain wetting, dispersing or emulsifying agents of the ionic or non-ionic type, for example sulphoricinoleates, quaternary ammonia derivatives of products based on ethylene oxide condensates, such as condensates of ethylene oxide with octylphenol, or fatty acid esters of anhydrosorbitols which have been rendered soluble by etherification of the free hydroxyl radicals by condensation with ethylene oxide. it is preferable to use agents of the non-ionic type because they are not sensitive to electrolytes. When emulsions are required, the compound may be used in the form of self-emulsifying concentrates containing the active substance dissolved in the emulsifying agent or in a solvent containing an emulsifying agent compatible with the compound and solvent, a simple addition of water to such concentrates producing compositions ready for use.

These compositions, which can be solid or liquid, optionally contain one or more other pesticides, such as insecticides or fungicides, compatible with the compounds of general formula 1 and with the diluent or adjuvant.

The new dihydrodibenzoazepine derivatives of general formula I are preferably employed as fungicides in a quantity of 25 to g. of active compound per hectolitre of water. in the field the compounds can be ap plied at the rate of 25 to 75 g. per hectare.

The following Examples illustrate the invention.

EXAMPLE 1 Ethyl chloroformate (5.7 g.) is added to a solution of S-methyl- Ill-amino 10,1 Ldihydrodibenzol b,f]azepine 1 1.2 g.) in anhydrous pyridine (100 cc.), the temperature being maintained at -20C. The reaction mixture is kept at 20C. for 1 hour and then at 2C. for 1 hour. The mixture is then taken up in distilled water (700 cc.) and twice extracted with diethyl ether (total 200 cc.). The ethereal solution is successively washed with distilled water (100 cc.), twice with 5N hydrochloric acid (total 100 cc.) and three times with distilled water (total 300 cc. The ethereal solution is dried over an hydrous sodium sulphate and evaporated. The residue (13.1 g.) is dissolved in boiling diisopropyl ether (25 cc.). After cooling at 2C. for 3 hours, the crystals which have formed are filtered off, twice washed with ice-cold diisopropyl ether (20 cc.) and dried under reduced pressure (20 mmllg). 5-Methyl-l0- ethoxycarbonylamino-10,l 1-dihydrodibenzo[ b,f}azepine (11.6 g.), melting at C., is obtained.

5-Methyl-l0-amino-l0,l 1-dihydrodibenzo{b,f}azepine employed as startingmaterial can be obtained as follows:

5 Methy1-l0-oxo-l0,l 1-dihydrodibenzo[b,f]azepine, melting at 104C. is prepared in accordance with British Pat. No. 961,444;

S-Methyl-lO-hydroxyimino10,1 l-dihydrodibenzolbflazepine (53.3 g.), melting at 196C, is prepared by reaction of an excess of hydroxylamine with 5- rnethyl-l0-oxo-l0,l1-dihydrodibenzo[b,f]azepine (60 g.) in an aqueous methanol medium under reflux;

5-Methyl-l0-amino-l0,l l-dihydrodibenzo[b,f]azepine (l 1.5 g.) melting at 96C., is prepared by reduction of S-methyl-10-hydroxyimino-l0,l l-dihydrodibenzo[b,f]azepine (19 g.) by means of sodium (13 g.) in butanol at 100C.

EXAMPLE 2 A solution of methyl chloroformate (2.95 g.) in anhydrous benzene (20 cc.) is added at about 20C. to a solution of S-methyI-IOamino-IOJ l-dihydrodibenzo- [b,f]azepine (7.0 g.) and triethylamine (3.16 g.) in anhydrous benzene (70 cc.). The reaction mixture is left at 20C. for about 20 hours and is then taken up in distilled water (100 cc.) and diethyl ether (100 cc.). Insoluble matter (0.3 g.), melting at 260C, is filtered off. The organic solution is washed with distilled water (100 cc.), twice with 2N methanesulphonic acid (total 50 cc.), and three times with distilled water (total cc.), dried over anhydrous magnesium sulphate and then evaporated. The residue (7.8 g.) is taken up in diethyl ether (l00 cc.) and a further amount of insoluble matter (05 g.), melting at 260C, is filtered off. After evaporation of the filtrate the residue (7.1 g.) is dissolved in boiling diisopropyl ether (50 cc.). After cooling at 2C. for 17 hours, the crystals which have formed are filtered off, washed three times with diisopropyl ether (total 15 cc.) and dried under reduced pressure (20 mm.l-lg). The resulting product (6.5 g.), melting at l081 10C. is recrystallised from methanol (25 cc.) to yield S-methyl-lO-methoxycarbonylamino-10,] l -dihy- 5 drodibenzo[b,f}azepine (4.5 g.) melting at l 1 8- 120C.

EXAMPLE 3 A solution of ethyl chloroformate (5.4 g.) in anhydrous benzene (30 cc.) is added at 3C., over a period of 30 minutes, to a solution of l-amino-l0,1l-dihydrodibenzo[b,f]azepine (10.5 g.) and triethylamine (5.0 g.) in anhydrous benzene (150 cc.). The reaction mixture is left for about 4 hours at 20C. and is then treated with distilled water (150 cc.), 2N sodium hydroxide solution (25 cc.) methylene chloride (100 cc.) and diethyl ether (100 cc.). Insoluble matter (2.5 g.), melting at 200C, is filtered off. The organic solution is washed three times with distilled water (total 150 cc.), twice with 2N methanesulphonic acid (total 150 cc.), twice with a 5% (w/v) sodium bicarbonate solution (total 50 cc.), and then five times with distilled water (total 125 cc. The organic solution is dried over anhydrous sodium sulphate and then evaporated. The residue (10.5 g.) is taken up in diethyl ether (150 cc.); an insoluble material (1.1 g.), melting at 195C., is filtered off. The filtrate is evaporated. The residue (8.6 g.) is dissolved in a 15 85 (parts) by volume mixture of ethyl acetate and cyclohexane (280 cc.), and the resulting solution is chromatographed through a 0.2 0.5 mm. silica gel column (silica: 50 g.; column diameter: 18 mm.). Elution with the same solvent yields a first fraction of 300 cc. which is discarded, and then a second fraction of 300 cc.', concentration of this second fraction yields lO-ethoxycarbonylamino-10,1 l-dihydrodibenzo{b,f]azepine (6.4 g.) in the form of an oil.

Analysis: Calculated N 9.92

Found: 9.6 9.7

-Amino-l0,lldihydrodibenzolb,f]azepine employed as starting material can be obtained as follows:

lO-Methoxy-dibenzo[b,f]azepine (melting at 125C.) is prepared in accordance with the method described in the specification of British Pat. No. 943,277 entitled Dibenz[b,f]azepines and process for their preparation granted to J. R. Geigy AC. on an application filed Nov. 16, 1960.

l0-Oxo-l0,1 l-dihydrodibenzo[b,f]azepine (8.1 g.), melting at 141C., is prepared by the action of dilute hydrochloric acid on l0methoxy-dibenzo[b,f]azepine (14.0 g.).

l0-Hydroxyimino-10,l l-dihydrodibenzo[b,f]azepine (6.1 g.), melting at 168C, is prepared by reaction of an excess of hydroxylamine with l0-oxo-l0,l l-dihydrodibenzo[b,f]azepine (8 g.) in aqueous ethanol under reflux;

l0-Amino-l0,ll-dihydrodibenzo[b,f]azepine (2.4 g.), melting at 123C. is prepared by reaction ofsodium amalgam (205 g), containing 2.5% by weight of sodium, with l0-hydroxyimino-l0,l l-dihydrodibenzo[b,- f]azepine (6.1 g.) in ethanol.

EXAMPLE 4 Propyl chloroformate (4.5 g.) is added to a solution of S-methyl- IO-amino- 10,1 l-dihydrodibenzo[b,f]azepine (7.8 g.) in anhydrous pyridine (70 cc.) the temperature being maintained at 20C. The reaction mixture is kept at 20C. for 1 hour and then at 2C for 1 hour, and is then taken up in distilled water (500 cc.) and twice extracted with diethyl ether (total 300 cc.). The ethereal solution is successively washed three times with 2N hydrochloric acid (total 300 cc.) and then twice with distilled water (total 200 cc.). The ethereal solution is treated with vegetable charcoal (0.4 g.), dried over anhydrous sodium sulphate and evaporated. The residue (9.8 g.) is dissolved in ethanol (40 cc.) at about 40C., and distilled water (40 cc.) is then gradually added to the solution obtained. After standing for 4 hours at 25C. followed by 16 hours at 2 C., the crystals which have formed are filtered off, washed with a mixture of ethanol and water (1 l by volume; 15 cc.), and and dried under reduced pressure (20 mm.Hg) to yield 5-methyl-10- propoxycarbonylaminol 0,1 l-dihydrodibenzo[b,f]azepine (8.0 g.) melting at -72C. (instantaneous melting).

EXAMPLE 5 lsopropyl chloroformate (3.3 g.) is added to a solution of 5-methyl-l0-amino-l0,l l-dihydrodibenzo[b,- flazepine (5.6 g.) in anhydrous pyridine (50 cc.), the temperature being kept at 20C. The reaction mixture is kept at 20C. for l hour, and then taken up in distilled water (400 cc.) and extracted three times with diethyl ether (total 150 cc.). The ethereal solution is successively washed three times with distilled water (total 150 cc.), three times with N hydrochloric acid (total 150 cc.), and five times with distilled water (total 150 cc.), and is then dried over anhydrous sodium sulphate and evaporated. The residue (6.1 g.) is dissolved in boiling diisopropyl ether (20 cc.). After standing for l6 hours at 2C., the crystals which have formed are filtered off, washed with ice-cold diisopropyl ether (8 cc.) and then twice with petroleum ether (boiling point 40-65C.; total 20 cc.), and dried under reduced pressure 20 mm.Hg). 5-Methyl-l0' isopropoxycarbonylamino- 10,1 l-dihydrodibenzo[ b,- flazepine (5.1 g.), melting at 91C., is thus obtained.

EXAMPLE 6 Butyl chloroformate (5.0 g.) is added to a solution of 5-methyl-l0-amino-10,l ldihydrodibenzo[b,f]azepine (7.8 g.) in anhydrous pyridine (70 cc.), the temperature being kept at 20C. The reaction mixture is kept at 20C. for 1 hour and then at 2C. for 1 hour. The reaction mixture is then taken up in distilled water (500 cc.) and extracted three times with diethyl ether (total 210 cc.). The ethereal solution is successively washed three times with distilled water (total 150 cc.), twice with 2N hydrochloric acid (total cc.), and four times with distilled water (total 200 cc.). The ethereal solution is treated with vegetable charcoal (0.1 g.), dried over anhydrous sodium sulphate and evaporated. The residue (10.6 g.) is dissolved in boiling petroleum ether (boiling point 4065C.; 30 cc.). After standing for 3 hours at 2C., the crystals which have formed are filtered off, washed twice with ice-cold petroleum ether (boiling point 40-65C.; total 20 cc.), and dried under reduced pressure (20 mm.Hg) to yield 5-methyl-10 butoxycarbonylamino-10,1 l-dihydrodibenzol b,f}azepine (10.1 g.) melting at 77C.

EXAMPLE 7 lsobutyl chloroformate (5.0 g.) is added to a solution of 5-methy1l0 amino-10,1 1-dihydrodibenzo[b,flazepine (7.8 g.) in anhydrous pyridine (70 cc.), the tem perature being kept at 20C. The reaction mixture is kept at 20C. for 1 hour and then at 2C. for 1 hour. The reaction mixture is then taken up in distilled water (500 cc.) and extracted three times with diethyl ether (total 150 cc.). The ethereal solution is successively washed three times with distilled water (total 150 cc. twice with 2N hydrochloric acid (total 100 cc.) and three times with distilled water (total 300 cc.). The ethereal solution is dried over sodium sulphate and evaporated. The residue (105 g.) is dissolved in boiling ethanol (30 cc.), and distilled water (25 cc.) is then gradually added to the resulting solution. After standing for 2 hours at 2C., the crystals which have formed are filtered off, washed with a mixture of ethanol and water (1 1 by volume; 20 cc.) and dried under re duced pressure (20 mm.Hg) to yield 5-methyl-10- isobutoxycarbonylaminol0,1l-dihydrodibenzolb; flaxepine (9.9 g.) melting at 86C.

EXAMPLE 8 Ethyl chloroformate (2.9 cc.) is added at 20C. to a solution of 5-cthyl-10-amino 10,1l dihydrodibenzoibflazepine (6.5 g.) in anhydrous pyridine (60 cc.) over the course of 10 minutes. The resulting suspension is stirred at 20C. for 1 hour and then at 2C. for l hour 30 minutes. The reaction mixture is poured into ice-water (600 cc.). The oil which separates is twice extracted with diethyl ether (total 300 cc.). The combined ethereal solutions are twice washed with distilled water (total 300 cc.), then twice with N hydrochloric acid (total 300 cc.) and finally with a 2% (w/v) solution of sodium bicarbonate (150 cc.). The ethereal solution is dried over anhydrous magnesium sulphate and concentrated. The residue (7.4 g.) is distilled under reduced pressure to yield 5-ethyl-l0- ethoxycarbonylamino-10,11-dihydrodibenzolb,f]aze pine (5.7 g.). b.p. 192-l94C./O.9 mm.Hg.

5Ethyl- 10,1 1-dihydrodibenzo[b,f]azepine employed as starting material can be obtained as follows:

10-Methoxy-dibenzo[bflazepine is prepared as indi cated in Example 3.

5'Ethyl-10-methoxy-dibenzolbflazepine (15.4 g.). melting at 180C, is prepared by the action of sodium amide followed by ethyl iodide, in hexamethylphosphotriamide, on 10-methoxy-dibenzolb,flazepine (20 g.).

5-Ethyl-lO-oxo-l0,l 1-dihydrodibenzo[b,f]azepine (10.7 g.), melting at 120C, is prepared by the action of dilute hydrochloric acid on 5-ethy1-10methoxydibenzo[b,f]azepine (12.7 g.).

5-Ethy1- l 'hydroxyiminol 0,1 l -dihydrodibenzo[b,- flazepine (10.8 g.), melting at 207C, is prepared by reaction of an excess of hydroxylamine with -ethy1-10- oxo-l0,l1dihydrodibenzo[b.flazepine (10.5 g.).

5-Ethyl10 amino-10,1ldihydrodibenzo[b,f}azepine (6.7 g), melting at 89C., is prepared by reaction of so dium amalgam (335 g.), containing 2.5% by weight of sodium, with S-ethyl-hydroxyimino10,l ldihydrodibenzo(b,f]azepine (10 g.) in ethanol.

EXAMPLE 9 Following the procedure described in Example 8 but reacting 5methy1-l0amino-10,l l-dihydrodibenzo[b,- flazepine (6.7 g.) and heptyl chloroformate (5.7 g.) in anhydrous pyridine (60 cc. S-methyl- 1 0- 8 heptyloxycarbonylamino- 10,1 1 dihydrodibenzo[ b,- flazepine (8.6 g.), melting at 78C., is obtained.

5-Methyl-l0-amino-10,1 1 dihydrodibenzo[b,f]azepine employed as starting material can be obtained as indicated in Example 1.

EXAMPLE 10 Following the procedure described in Example 8 but reacting 5-propyl-10-amino-10,i l-dihydrodibenzo[ b,- f]azepine (5.9 g.) and ethyl chloroformate (2.7 g.) in anhydrous pyridine (65 cc.), 5-propy1-10- ethoxycarbonylamino-10,l 1-dihydrodibenzo[b,f]azepine (5i g.) is obtained.

Analysis: Calculated N 8.63

Found: 84

5-Propyl-10-amino-10,l 1dihydrodibenzo[b,f]azepine employed as starting material can be obtained as follows:

1U-Methoxy-dibenzolb.flazepine is prepared as indicated in Example 3.

5Propyl-10-rnethoxy-dibenzoibflazepine 18 g. melting at 100C, is prepared by the action of sodium amide followed by propyl bromide on 10-methoxydibenzo[b,f1azepine (20 g.) in a mixture of toluene and hexamethylphosphotriamide (10 l by volume) at -100C.

5-Propyl-10-oxo- 10,1 1-dihydrodibenzo[b,flazepine (16.7 g.), melting at 6062C. is prepared by the action of 2N hydrochloric acid on 5-propy1-10-methoxydibenzolbflazepine (18 g.) under reflux for 1% hours.

5-Propyl-l0-hydroxyimino-l0,11-dihydrodiben zolb,f]azepine (17.2 g.). melting at C, is prepared by the action of hydroxylamine hydrochloride (9.25 g.) and sodium acetate trihydrate (18.1 g.) on S-propyl- ]0-oxol0,11-dihydrodibenzolbflazepine (16.7 g.) in a mixture of ethanol and water (3 1 by volume) under reflux for 5 hours.

5 -Pr0pyllG-amino- 10,1 1-dihydrodibenzo[b,f]azepine, the fumarate of which melts at 212-2l5C., is prepared by reduction of S-propyl-lO-hydroxyimino- 10,11-dihydrodibenzolb,f]azepine by means of sodium in butanol at 100C.

EXAMPLE 11 Hexyl chloroformate (5.25 g.) is added over the course of 5 minutes, at -20C., to a solution of 10- amino-10,1ldihydrodibenzolb,f]azepine (6.3 g.) in anhydrous pyridine (60 cc.). The resulting suspension is stirred for 2 hours at 20C. and then for 2 hours at +2C. The reaction mixture is poured into distilled water (500 cc.) The oil which separates is extracted three times with diethyl ether (total 450 cc). The combined ethereal solutions are twice washed with N by drochloric acid (total 300 cc.) and then twice with distilled water (total 200 cc.). The ethereal solution is dried over anhydrous magnesium sulphate and concen trated. The residue (8.3 g.) is dissolved in cyclohexane (800 cc.) and the resulting solution is chromatographed on silica (85 g; column diameter 2.3 cm). Elution is carried out with a mixture of cyclohexane and ethyl acetate (9 1 by volume). After concentrating the eluates under reduced pressure, 10 -hexyloxycarbonylamino-10,1l-dihydrodibenzolb,flazepine (7.7 g.) is obtained.

Analysis: Calculated C 74.53 H 7.74 N 8.28

Found: 73.2 7.3 7.7.

5-Amino-10,1 1-dihydrodibenzo[b,f]azepine employed as starting material can be obtained as indicated in Example 3.

EXAMPLE 12 Following the procedure described in Example 11 but reacting IO-aminol 0,1 1-dihydrodibenzo[b,f]azepine (6.3 g.) and methyl chloroformate (3.0 g.) in anhydrous pyridine (60 cc.), -methoxycarbonylamino- 10,11-dihydrodibenzo[b,f]azepine (4.0 g.) is obtained.

Following the procedure described in Example 11 but reacting 10-amino-10,11-dihydrodibenzo[b,f}azepine (6.3 g.) and propyl chloroformate (3.7 g.) in anhydrous pyridine (60 cc.), lO-propoxycarbonylamino- 10,1 l-dihydrodibenzo[b,f]azepine (6.8 g.) is obtained.

Analysis: Calculated C 72.96

Found: 728

EXAMPLE 14 Following the procedure described in Example 1 l but reacting l0-amino-10,1l-dihydrodibenzo[b,f]azepine (6.3 g.) and butyl chloroformate (4.4 g.) in anhydrous pyridine (60 cc.), IO-butoxycarbonylamino- 10,11-dihydrodibenzo(b,f]azepine (8.0 g.) is obtained.

Following the procedure described in Example 11 but reacting l0-amino-10,ll-dihydrodibenzo[b,f]azepine (6.3 g.) and pentyl chloroformate (4.8 g.) in anhydrous pyridine cc.), l0-pentyloxycarbonylamino 60 10,1 l-dihydrodibenzo[b,f]azepine (7.5 g.) is obtained.

Analysis: Calculated C 74.05

Found: 73.8

EXAMPLE 16 Following the procedure described in Example 11 but reacting l0-amino-10,1 1-dihydrodibenzo[b,f]azepine (6.3 g.) and isopropyl chloroformate (4.1 g.) in anhydrous pyridine (60 cc. 10 isopropoxycarbonylamino- 10,1 l-dihydrodibe nzo[b,- f]azepine (5.5 g.), melting at 106C, is obtained.

EXAMPLE 17 Following the procedure described in Example 11 but reacting l0-amino-10,11-dihydrodibenzo[b,f]azepine (6.7 g.) and isobutyl chloroformate (4.5 g.) in anhydrous pyridine (60 cc. 10- isobutoxycarbonylamino- 1 0,1 l-dihydrodibenzo[b,- f]azepine (9.1 g.) is obtained.

Analysis: Calculated C 73.52 H 7.14 N 9.03

Found: 73.8 7.4 8.9

EXAMPLE 18 Sodium lignosulphite (25 g), kaolin (470 g.) and Tween 80" (5 g.) ["Tween" is a registered Trade Mark] are added to 5-methyl-10- ethoxycarbonylamino-10,l l-dihydrodibenzo[b,f]azepine (500 g.). After grinding and sieving, the resulting powder is used, after dilution with water in the ratio of g. of powder per 100 litres of water, to protect plants against attacks by mildew.

We claim:

1. A fungicidal composition comprising, as active ingredient, a fungicidally effective amount of a 10,11- dihydrodibenzo [b,f] azepine derivative of the formula llIH-COOR wherein R represents hydrogen or alkyl of 1 through 5 carbon atoms and R, represents alkyl of 1 through 7 carbon atoms in association with a diluent or adjuvant compatible with the dihydrodibenzoazepine derivative and suitable for use in agricultural fungicidal compositions, the quantity of dihydrodibenzoazepine derivative in the composition being between 80 and 0.0005% by weight of the composition.

2. The fungicidal composition of claim 1 wherein R represents hydrogen, methyl, ethyl or propyl, and R, represents straight chain alkyi of 3 through 6 carbon atoms.

3. The fungicidal composition of claim 1 wherein said derivative is S-methyl-lO-propoxycarbonylamino- 10,1 l-dihydrodibenzo[ b,f]azepine.

4. The fungicidal composition of claim 1 wherein said derivative is S-methyl -10-butoxycarbonylamino- 10,1 1-dihydrodibenzo{b,f]azepine.

5. The fungicidal composition of claim 1 wherein said derivative is 10-hexyloxycarbonylamino-10,1 l-dihydrodibenzo[b,f]azepine.

6. The fungicidal composition of claim 1 wherein said drodibenzo[b,f]azepine. derivative is lO-propoxycarbonylamino-10,l l-dihy- 8. The fungicidal composition of claim 1 wherein said drodibenzo[b,f]azepine. derivative is lO-pentyloxycarbonylamino-l0,l l-dihy- 7. The fungicidal composition of claim 1 wherein said drodibenzo[b,f]azepine. derivative is lO-butoxycarbonylamino-l0,l l-dihy- 

1. A FUNGICIDAL COMPOSITION COMPRISING, AS ACTIVE INGREDIENT, A FUNGICIDALLY EFFECTIVE AMOUNT OF A 10,11-DIHYDRODIBENZO (B,F) AZEPINE DERIVATIVE OF THE FORMULA
 2. The fungicidal composition of claim 1 wherein R represents hydrogen, methyl, ethyl or propyl, and R1 represents straight chain alkyl of 3 through 6 carbon atoms.
 3. The fungicidal composition of claim 1 wherein said derivative is 5-methyl-10-propoxycarbonylamino-10,11-dihydrodibenzo(b, f)azepine.
 4. The fungicidal composition of claim 1 wherein said derivative is 5-methyl -10-butoxycarbonylamino-10,11-dihydrodibenzo(b, f)azepine.
 5. The fungicidal composition of claim 1 wherein said derivative is 10-hexyloxycarbonylamino-10,11-dihydrodibenzo(b,f)azepine.
 6. The fungicidal composition of claim 1 wherein said derivative is 10-propoxycarbonylAmino-10,11-dihydrodibenzo(b,f)azepine.
 7. The fungicidal composition of claim 1 wherein said derivative is 10-butoxycarbonylamino-10,11-dihydrodibenzo(b,f)azepine.
 8. The fungicidal composition of claim 1 wherein said derivative is 10-pentyloxycarbonylamino-10,11-dihydrodibenzo(b,f)azepine. 